Azo dyestuffs containing a quaternized pyrazolone radical



United States Patent 3,092,615. Patented June 4, 196 3 3,092,615 AZO DYESTUFFS CONTAINING A QUATERNIZED PYRAZOLONE RADICAL Georges Raymond Henry Mingasson and Marcelle Henriette Fer-rand, Paris, France, assignors to Compagnie Francaise des Matieres Color-antes, Paris, France, a

French company No Drawing. Filed June 29, 1960, Ser. No. 39,434

Claims priority, application France July 1, 1959 6 Claims. (Cl. 260-463) The present invention concerns new azo dyestuffs, process for their preparation and their use in the colouratioln of polymers or co-polyrners based on polyacrylonitn' e.

The new azo dyestufis of the present invention can be represented by the general formula:

in which R represents the radical of a diazotisable amine, R represents a hydrogen atom or an alkyl or aryl group, R represents an atom of hydrogen or an alkyl, aryl or alkoxycarbonyl group and A represents an anionic radical. The new azo dyestuffs can be obtained by coupling a diazo derivative of a diazotisable base, free from solubilizing groups, with a pyrazolone of the general formula:

in which R and R have the meanings given above and transforming the dyestufi obtained into a quaternary ammonium salt. The diazotisable bases can be substituted, with halogen atoms, or alkyl, alkoxy, nitro or cyano groups.

The coupling can be efiected in a medium consisting of sodium acetate-acetic acid, or in an alkaline medium. The transformation into quaternary ammonium salts can be effected by the action of an alkylating agent, for example a dialkyl sulphate, an alkyl halide or an arylsulphonyl ester on the dyestutt in solution in an inert solvent.

The quaternary character of the dyestufis thus obtained is confirmed by the fact that they are soluble in water,

while the original dyestuffs are practicably insoluble in an aqueous acid medium; on the other hand they are not precipitated from their aqueous solutions by the addition of a mineral base such as caustic soda.

The new azo dyestuffs of the invention dye synthetic fibres based on polymers or co-polymers of acrylonitrile in bright shades going from greenish yellow to red, which are very fast to light and moisture tests. They possess moreover the property that they do not dye wool.

The following examples illustrate the invention withbut limiting it. The parts are expressed in weight except where otherwise indicated.

Example 1 parts of dyestuff obtained by coupling the diazo derivative of aniline with 3-methyl-S-pyrazolone are dissolved .under reflux in 125 parts of dry chlorobenzene. There is added slowly with agitation 16 parts of dimethyl sulphate diluted with 10 parts of chlorobenzene. Boiling is effected -for :1 /2 hours and the solvent is driven off by steam. The solution of the dyestuff is filtered, and after cooling the dyestutf is precipitated by the addition of salt and zinc chloride. It is filtered and dried.

Example 2 A dyebath is prepared by dissolving 0.5 partof the dyestufr of Example 1 in 2 parts of water. There is added 2 parts of sulphuric acid and the dyebath is heated to 50 C. There is introduced into this bath pants of the fibre based on acrylonitrile, known on the market as Orlon. The bath is brought to boiling and dyeing is elfected for an hour at this temperature. The fibre is coloured a greenish yellow shade. Under the same conditions of dyeing the dyestuff does not dye wool.

Other examples are summarised in the following table, in which the shades indicated are the shades obtained on synthetic fibres based on polymers or co-ipolymers of acrylonitrile.

Example Diazotised Base Copulent Shade 3 o-toluidine 3-methyl-5 pyrazyellow.

olone.

' golden yellow. m-xylidine o reddish yellow. p-xylidine. golden yellow. o-chlorani.l ine. Do

greenish yellow. golden yellow. orange yellow. orange.

o-nitraniline reddish yellow.

4-nitro 2methyld0 Do.

aniline.

4-nitro-2-methoxy- .do orange yellow.

aniline.

2:? iichloroanldo greenish yellow.

fl-naphthylaminedo orange.

aniline 3-ethoxycarbonylgolden yellow.

S-pyrazolone. p-anisidine "do scarlet. aniline 3-pll1eny1-5-pyrazgolden yellow.

0 one.

ptoluidine do reddish yellow.

p-anisldine do orange red.

aniline 1-phenyl-3-methylgreenish yellow.

5-pyrazolone. p-toluidme do golden yellow. p-anisidine do orange.

Example 25 By working as in Example 1, but by replacing the dimethyl sulphate by 25 parts of the methyl ester of paratoluene sulphonic acid there is obtained, after removal of the solvent in steam, a solution of dyestufl which is precipitated by salting and addition of zinc chloride. The dyestufi thus obtained has the same characteristics as the dyestuff of Example 1.

We claim:

1. A20 dyestutf of the general formula:

in which R represents a member selected from the group consisting of phenyl, naphthyl, methyl substituted phenyl, methoxy substituted phenyl, chloro substituted phenyl, and nitro substituted phenyl radicals, R represents a member selected from the group consisting of the hydrogen atom and the phenyl radical, R represents a member selected from the group consisting of methyl, phenyl and ethoxycarbonyl groups, and A represents a monovalent anion.

2. The "compound of the fo ula 5."Ihe eomoound of the formula moo I N N-o-o-om H0g\ /I Ee-0H3 N 5 C N N-oo-om 'Ho-0 NOH A9 as A H 10 wher eA represents 'a monovalent anion.

, 3. The compound of the formula V where A represents a monovalent anion. 3 0*01'1 6. The compound of the formula HO-O N-CH: 15 1 OH;OON='N(I.?(HJCHa HO-O N-CH e a where A represents a monoualent aniou. I A6 4.'The compound of the formula where A represents a mouoyalent anion.

9 I References Cited in the file of this patent so V UNITED STATES PATENTS 2,883,373 Bossard et 51. Apr. 21, 1959' where A represents a monovalent anion. 2,972,508 Kruckenberg et a1 Feb. 21, 196-1 7 

1. AZO DYESTUFF OF THE GENERAL FORMULA: 